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C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms

C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen

C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation

C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene

C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms

C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons

C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation

C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond

C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms

C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring

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C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms

C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction

C07C4/06—Catalytic processes

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C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms

C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation

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C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms

C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation

C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31

C07C5/2226—Catalytic processes not covered by C07C5/23 - C07C5/31 with inorganic acids; with salt or anhydrides of acids

C07C5/224—Acids of phosphorus; Salts thereof; Phosphorus oxides

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C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms

C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation

Abstract

Crystalline molecular sieves having three-dimensional microporous framework structures of ELO2, AlO2, SiO2 and PO2 framework oxide units are disclosed. The molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (ELw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ELw Alx Py Siz)O2 ; "EL" represents at least one element capable of forming a framework oxide unit; and "w", "x", "y" and "z" represent the mole fractions of element(s) "EL", aluminum, phosphorus and silicon, respectively, present as framework oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

Description

This is a division of our copending application Ser. No. 600,312, filed Apr. 13, 1984, now U.S. Pat. No. 4,793,984.

FIELD OF THE INVENTION

The instant invention relates to a novel class of three-dimensional microporous crystalline molecular sieves, to the method of their preparation and to their use as adsorbents and catalysts. The invention relates to novel molecular sieves having at least one element capable of forming a framework oxide units, e.g., "ELO2 ", with tetrahedral oxide units of aluminum (AlO2-), phosphorous (PO2+) and silicon (SiO2). These compositions may be prepared hydrothermally from gels containing reactive compounds of silicon, aluminum and phosphorus and at least one additional element capable of forming a framework oxide unit, and preferably at least one organic templating agent which may function in part to determine the course of the crystallization mechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO2 and SiO2 tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.

Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO2 tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolite are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6 Å or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral frame work containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,319,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO2 and PO2 tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.

In copending and commonly assigned application Ser. No. 400,438, filed July 26, 1982 (now U.S. Pat. No. 4,440,871), there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensionally crystal framework of PO2+, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:

mR: (Six Aly Pz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Six Aly Pz)O2 and has a value of per zero to 0.3; the maximum value of each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represents the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.

In copending and commonly assigned application Ser. No. 480,738, filed Mar. 31, 1983 (now U.S. Pat. No. 4,500,651) there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:

mR:(Tix Aly Pz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Tix Aly Pz)O2 and has a value of between zero and about 5.0; and "x", "y" "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,334, filed July 15, 1983 (now U.S. Pat. No. 4,567,029), there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO2, AlO2 and PO2 tetrahedral units and having an empirical chemical compositions on an anhydrous basis expressed by the formula:

mR:(Mx Aly Pz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Mx Aly Pz)O2 and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,335, filed July 15, 1983 (now U.S. Pat. No. 4,683,217), there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO2, AlO2 and PO2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula

mR:(Fex Aly Pz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fex Aly Pz)O2 and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fraction of the iron, aluminum and phosphorus, respectively, present as tetrahedral oxides. The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including the aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of certain species and by the existence of species heretofore unknown for binary and ternary molecular sieves.

The instant invention relates to new molecular sieve compositions having at least one element other than silicon, aluminum and phosphorus where such element is capable of forming a framework oxide unit with AlO2-, PO2+, and SiO2 tetrahedral oxide units.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the insant compositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class of molecular sieves in which at least one element capable of forming a framework oxide unit is provided to form crystal framework structures of SiO2, AlO2- and ELO2n units wherein "EL" represents at least one element present as a framework oxide unit "ELO2n " with charge "n" where "n" may be -3, -2, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use of adsorbents and catalysts.

The members of this novel class of compositions have crystal framework structures of SiO2, AlO2, PO2+ and ELO2n framework oxides units, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (ELw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ELw Alx Py Siz)O2 and has a value from zero to about 0.3; "EL" represents at least one element capable of forming a framework oxide unit as hereinafter described; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxide units. "EL" denominates the elements present in addition to aluminum, phosphorus and silicon and may be a single element or may be two or more elements such that the molecular sieves contain one or more framework oxide units "ELO2n " in addition to framework tetrahedral oxide units SiO2, AlO2- and PO2+.

The molecular sieves of the instant invention will be generally referred to by the acronym "ELAPSO" to designate element(s) "EL" in an oxide framework of SiO2, AlO2-, PO2+ and ELO2n oxide units. Actual class members will be identified by replacing the "EL" of the acronym with the element(s) present as a ELO2n oxide unit(s). For example "CoAPSO" designates a molecular sieve comprised of SiO2, AlO2-, PO2+ and CoO2-2 (and/or CoO2-1) framework oxide units, and "CoZnAPSO" designates a molecular sieve having SiO2, AlO2-, PO2+, CoO2-2 (and/or COO2-1) and ZnO2-2 framework oxide units to identify various structural species which make up each of the subgeneric classes, each species is assigned a number and is identified as "ELAPSO-i" wherein "i" is an integer. This designation is an arbitrary one and is not intended to denote structural relationship to another material(s) which may also be characterized by a numbering system.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class of three-dimensional microporous crystalline molecular sieves in which at least one element capable of forming a framework oxide unit is provided to form crystal framework structures of SiO2, SiO2-, PO2+ and ELO2n framework oxide units wherein "EL" represents at least one element capable of forming a framework oxide unit "ELO2n " with charge "n" where "n" is -3, -2, -1, 0 or +1. These molecular sieves exhibit ion-exchange, adsorption and catalytic properties and accordingly find wide use as adsorbents and catalysts.

The ELAPSO compositions are formed with elements capable of forming framework oxide units in the presence of SiO2, SlO2- and PO2+ tetrahedral oxide units where element "EL" is at least one element capable of forming a three dimensional oxide framework in the presence of aluminum, phosphorus and silicon oxide units, and has a mean "T-O" distance in tetrahedral oxide structures of between about 1.51 Angstroms and about 2.06 angstroms, has a cation electronegativity between about 125 kcal/g-atom and about 310 kcal/g-atom and is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures where the "M-O" bond dissociation energy, D°, is greater than about 59 kcal/mole at 298° K. The use of "M" in the aforementioned discussion on bond energies is one of convenience since the prior art has heretofore employed "M" to designate the element (EL) bonded to oxygen. For the purposes of discussion herein any reference to M-O-P, M-O-Al, M-O-M or M-O refers to the substitution of element(s) "EL" for the "M" designation. The "T-O" distance denominates the bond length of the "T-O" bond where "T" is element(s) "EL" occupying the tetrahedral cation site and is related to the Shannon/Prewitt crystal to ionic radii. Elements known to occur in tetrahedral coordination with oxygen are discussed in: Joseph V. Smith, "Feldspar Minerals", Springer-Verlag, Berlin, N.Y., Vol. I, pp. 55-65 and 106-113 (1974); R. D. Shannon, Acta. Cryst., A32, p. 751 (1976); R. D. Shannon, C. T. Prewitt, Acta. Cryst., B25, p. 925 (1969); and F. Donald Bloss, "Crystallography and Crystal Chemistry", Holt, Rinehart and Winston, Inc., N.Y., pp. 278-279 (1971). The "T-O" distance is calculated according to the procedures heretofore employed and as discussed in, R. D. Shannon, Acta Cryst., A32, p. 751 (1976) and R. D. Shannon, C. T. Prewitt, Acta Cryst., B25, p. 925 (1969), based, respectively, on the ionic and crystal radius of oxide ion , O2-, of 1.40 Angstroms and 1.26 Angstroms. The cation electronegativity of element(s) "EL" is determined consistent with the procedure set forth in A. S. Povarennykh, "Crystal Chemical Classification of Minerals", Vol. I, translation from Russian by J. E. S. Bradley, Plenum Press, New York-London, p. 32 (1972). The bond dissociation energy of "M-O" is determined according to the procedures discussed in: V. I. Vedeneyve, L. V. Gurvich, V. N. Kondrat'Yev, V. A. Medvedev and Ye. L. Frankevich, "Bond Energies, Ionization Potentials and Electron Affinities," New York, ST. Martins Press, English Translation, p. 29ff (1966); "The Oxide Handbook", 2nd Ed., G. V. Samsonov, ED., translation from Russian by R. K. Johnston, IFI/Plenum Data Company, pp. 86-90 (1982); and "Bond Dissociation Energies in Simple Molecules", B. deB. Darwent, NSRSSONBS 31, U.S. Dept. Of Commerce, National Bureau of Standards, pp. 9-47 (1970).

Further embodiments of the instant invention relates to the molecular sieves as above defined being characterized by element(s) "EL" characterized by at least one of the following criteria:

(1) "EL" is characterized by an electronic orbital configuration selected from the group consisting of d0, d1, d2, d5, d6, d7, or d10 where the small crystal field stabilization energy of the metal ligand "OM" favors tetrahedral coordination of element EL ("EL" denominated here also as "M") with O2-, as discussed in "Inorganic Chemistry" J. E. Huheey, Harper Row, p. 348 (1978):

(2) "EL" is characterized as capable of forming stable oxo or hydroxo species in aqueous solution as evidenced by a first hydrolysis constant, K11, greater than 10-14, as discussed in "The Hydrolysis of Cations", C. F. Baes and R. E. Mesmer, John Wiley & Sons (1976);

(3) "EL" is selected from the group of elements known to occur in crystal structure type geometrically related to the different silica modifications, quarts, cristobalite or tridymite, as discussed in E. Parthe, "Crystal Chemistry of Tetrahedral Structures", Gordon and Breach, New York, London, pp. 66-68 (1964); and

(4) "EL" is an element which in its cation form is classified by Pearson, (J. E. Huheey, "Inorganic Chemistry", Harper & Row, p. 276 (1978)) as "hard or borderline" acids which interact with the "hard" base O2- to form more stable bonds than the cations classified as "soft" acids.

In one embodiment of the invention element "EL" is preferably at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc.

The relative amounts of silicon, aluminum phosphorus and element(s) "EL" are expressed by the empirical chemical formula (anhydrous):

The molecular sieves of the instant invention have three-dimensional microporous crystalline framework structures of ELO2n, AlO2-, PO2+ and SiO2 framework oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (ELw Alx Py Siz)O2

wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ELw Alx Py Siz)O2 and has a value of zero to about 0.3;

"EL" represents at least one element capable of forming a three dimensional oxide framework has a mean "T-O" distance in tetrahedral oxide structures of between about 1.51 Angstroms and about 2.06 Angstroms, has a certain electronegativity between about 124 kcal/g-atom to 310 kcal/g-atom and is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures where the "M-O" bond dissociation energy, D°, is greater than about 59 kcal/mole at 298° K.; and "w", "x", "y" and "z" represent the mole fractions of element(s) "EL", aluminum, phosphorus and silicon, respectively, present as framework oxide units. The use of "M" in the aforementioned discussion on bond energies is one of convenience since the prior art has heretofore employed "M" to dominate the element (EL) bonded to oxygen. For the purpose of discussion herein any reference to M-O-P, M-O-Al, M-O-M or M-O refers to the substitution of element(s) "EL" for the "M" designation. The mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of FIG. 1, said points A, B, C, D and E of FIG. 1 having the following values for "w", "x", "y", and "z":

where "p" is an integer corresponding to the number of elements "EL" in the (ELw Alx Py Siz)O2 constituent and is preferably an integer from one (1) to fourteen (14).

In a preferred subclass of the ELAPSO molecular sieves the values of "w", "x", "y" and "z", where "w" is as above defined, in the above formula are within the tetragonal compositional area defined by points, a, b, c and d of the ternary diagram which is FIG. 2, said points a, b, c and d representing the following values for "w", "x", "y" and "z";

While it is believed that the elements "EL", aluminum, phosphorus and silicon in the framework constituents are present in tetrahedral coordination with oxygen, i.e. as tetrahedral oxide units, it is theoretically possible that some fraction of these framework constituents are present in coordination with five or six oxygen atoms. The convenient reference herein to the framework oxide units are represented by formulae which indicate tetrahedral oxide units, although as above noted other tetrahedral coordination may exist. It is not, moreover, necessarily the case that all the elements "EL" of any given synthesized product be part of the framework in the aforementioned types of coordination with oxygen. Some of each constituent may be in some as yet undetermined form.

The ELAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.

ELAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing active sources of element(s) "EL", silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent which is preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali of other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogeneous pressure at an effective temperature which is preferably between about 50° C. and about 250° C., more preferably between 100° C. and 200° C., until crystals of the ELAPSO product are obtained, usually an effective crystallization line of from several hours to several weeks. Generally, effective crystallization times of from about 2 hours to about 30 days are employed with typically from 4 hours to about 20 days being employed to obtain ELAPSO product. The product is recovered by any convenient method such as centrifugation or filtration.

In synthesizing the ELAPSO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of molar ratios as follows:

AR: (ELy Als Pt Siu)O2 ; BH2 O

wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; "EL" represents at least one element, as herein before described, capable of forming a framework oxide unit, ELO2n, with SiO2, AlO2- and PO2+ tetrahedral oxide units; "n" has a value of -3, -2, -1, 0 or +1; and "r", "s", "EL", aluminum, phosphorus, and silicon respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions "r", "s", "t", and "u" are generally defined as being within the pentagonal compositional area defined by points E, F, G, H, and I of the ternary diagram of FIG. 3. Points E, F, G, H, and I of FIG. 3 have the following values for "r", "s", "t", and "u":

In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "r", "s", "t", and "u" such that (r+s+t+u)=1.00 mole, whereas in the examples the reaction mixtures may be expressed in terms of molar oxide ratios normalized to the moles of P2 O5. This latter form is readily converted to the former form by routine calculations by dividing the number of moles of each component (including the template and water) by the total number of moles of elements "EL", aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.

In forming reaction mixtures from which the EAPSO molecular sieves are formed an organic templating agent is preferably employed and may be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosulicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorus and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use of templating agents are the amines, quarterly phosphonium and quaternary ammonium compounds, the latter two being represented generally by the formulae R4 X+ wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C14 H32 N2) (OH)2 ]x wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents may either produce mixtures of the desired ELAPSOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents includes: tetramethylammonium; tetraethylammonium; tetrapropylammonium; tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylaminel; 2-methylpyridine; N,N-diemthylbenzylamine; N,N-dimethylethanolamine; chline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2,) octaine; N-methyldiethanolamine, M-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; ci-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of ELAPSO, i.e., a single templating agent may, with proper manipulation of the reaction conditions, direct the formation of several ELAPSO compositions, and a given ELAPSO composition can be produced using several different templating agents.

The source of silicon may be silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silica containing clays silicic acid or alkali metal silicate and mixtures thereof.

The most suitable phosphorus source yet found for the present process is phosphoric acid, but organic phosphats such as triethyl phosphate have been found satisfactory, and so also have crystalline or amorphous aluminophosphates such as the AlPO4 compositions of U.S. Pat. No. 4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphonium bromide do not, apparently, serve as reactive sources of phosphorus, but these compounds do functions as templating agents. Conventional phosphorus salts such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.

The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, aluminum-containing clays, sodium sluminate and aluminum trichloride, can be employed but are not preferred.

While not essential to the synthesis of ELAPSO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the ELAPSO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.

After crystallization of ELAPSO product may be isolated and advantageously washed with water and dried in air. The as-synthesized ELAPSO generally contains within its internal pore system at least one form of any templating agent employed in its formation. Most commonly this organic moiety, derived from any organic template, is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety may be an occuled molecular species in a particular ELAPSO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the ELAPSO product and must be removed by calcining the ELAPSO at temperatures of 200° C. to 700° C. to thermally degrade the organic species. In some instances the pores of the ELAPSO compositions are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof may be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of ELAPSO species wherein any organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula:

mR: (Mw Alx Py Siz)O2

has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of element(s) "EL", aluminum, phosphorous and/or silicon, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the syntheses process as a templating agent. For the purpose of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized ELAPSO material.

Since the present ELAPSO compositions are formed from AlO2-, PO2+, SiO2 and ELO2n framework oxide units which, respectively, have a net charge of -1, +1, 0 and "n", where "n" is -3, -2, -1, 0 or +1, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO2- tetrahedra and charge-balancing cations. In the instant compositions, an AlO2- tetrahedron can be balanced electrically either by association with a PO2- tetrahedron or a simple cation such as an alkali metal cation, a cation of the element "EL" present in the reaction mixture, or an organic cation derived from the templating agent. Similarly, an ELO2n oxide unit can be balanced electrically by association with PO230 tetrahedra, a simple cation such as an alkali metal cation, a cation of the metal "EL", organic cations derived from the templating agent, or other divalent or polyvalent metal cions introduced from an extraneous source. It has also been postulated that non-adjacent AlO2- and PO2+ tetrahedral pairs ca be balanced by Na+ and OH- respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC. (1971)].

The ELAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3 Å in diameter. Ion exchange of ELAPSO compositions will ordinarily be possible only after the organic moiety present as a result of synthesis has been removed from the pore system. Dehydration to remove water present in the as-synthesized ELAPSO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The ELAPSO materials will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.

In the examples a stainless steel reaction vessel is utilized which is lined with an inert plastic material, polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each ELAPSO composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the admixed reagents retain their identity in the intermediate mixture and in other cases some or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, unless otherwise specified, each intermediate mixture as well as the final reaction mixture was stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis using standard X-ray powder diffraction techniques. The radiation source is a highly-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2° (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed at 2θ where θ is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background, "Io " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.

Alternatively, the X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens D-500 X-ray powder diffractometers, Siemens Type K-805 X-ray source, available from Siemens Corporation, Cherry Hill, N.J., with appropriate computer interface.

As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about ±0.4° (denotes plus or minus 0.4) on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak, and very weak, respectively.

In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.

The molecular sieves of the instant invention may be characterized by their x-ray powder diffraction patterns and such may have one of the x-ray patterns set forth in the following Tables A through W, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

ELAPSO MOLECULAR SIEVE COMPOSITIONS

The ELAPSO molecular sieves of the invention may be prepared having one or more elements present as framework oxide units such that the ELAPSO molecular sieves contain framework oxide units "ELO2 ", ALO2-, PO2+ and SiO2 where "EL" denominates at least one element capable of forming a framework oxide unit with AlO2-, PO2+ and SiO2 tetrahedral oxide units. The following ELAPSO molecular sieves are representative of molecular sieves prepared according to the instant invention:

The reaction mixtures were prepared by forming a starting reaction mixture comprising the H3 PO4 and one half of the water. This mixture was stirred and the aluminum source (Alipro or CATAPAL) added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX-LS was then added to the resulting mixture and the new mixture blended until a homogeneous mixture was observed. The cobalt source (Co(Ac)2, Co(SO4) or mixtures thereof) was dissolved in the remaining water and combined with the first mixture. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction mixture) as placed in a lined (polytetrafluoroethylene) stainless stell pressure vessel and digested at a temperature (150° C., 200° C. or 225° C.) for a time. Alternatively, if the digestion temperature was 100° C. the final reaction mixture was placed in a lined (polytetrafluoroethylene) screw top bottle for a time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

EXAMPLES 1A TO 31A

CoAPSO molecular sieves were prepared according to the above described procedure and the coAPSO products determined by x-ray analysis. The results of examples 1A to 31A are set forth in Tables I-A and II-A. Tables I-A and II-A also contain examples AA to EA wherein X-ray analysis of the reaction mixture product did not show CoAPSO products.

In the Tables I-A and II-A, the reaction mixtures are described as the ratio of molar oxides:

eR:fCoO:0.9Al2 O3 :0.9P2 O5 :gSiO2 :5OH2 O

where "e", "R", "f" and "e" are as above defined. Examples were prepared using this reaction mixture unless otherwise noted in Tables I-A to II-A. The values for "e", "f" and "g" are given in Tables I-A and II-A.

Examples 32A to 61A were carried out using di-n-propylamine as the organic templating agent. The preparative procedure was as above described except that in examples 39A to 45A and 53A to 61A the preparative procedure was modified such that the cobalt acetate was added to the phosphoric acid and water, followed by addition of the aluminum source, silicon source and then the organic templating agent. The aluminum source in examples 32A to 45A, 60A and 61A was aluminum isoproproxide and in examples 46A to 59A the aluminum source was CATAPAL. The reaction mixtures for examples 32A to 61A are described in terms of the molar oxide ratios: ePr2 NH:0.2CoO:0.9Al2 O3 :0.9P2 O5 ;0.2SiO2 :5OH2 O where "e" is the moles of template Pr2 NH and where "e" was one (1) for examples 32A to 35A, 42A to 45A, 49A to 52A, 56A to 61A and "e" was two (2) for examples 36A to 41A, 46A to 48A, 53A to 55A. Examples FA, GA, HA and IA are reaction mixtures where X-ray analysis of the reaction products did not show CoAPSO products. Examples 32 to 61 and F, G, H, and I are set forth in Table III.

Examples 62A to 83A were carried out according to the preparative procedure employed in examples 1A to 31A except that the organic templating agent was the TEAOH (tetraethylammonium hydroxide). The reaction mixtures for examples 62A to 83A were:

1.0TEAOH:fCoO:0.9Al2 O3 :0.9P2 O5 :gSiO2 :5OH2 O

wherein "f" was 0.2 except that "f" was 0.1 for examples 78A to 79A and was 0.05 for examples 80A to 83A; and g was 0.2 for examples 62A to 70A and was 0.6 for examples 71A to 83A. The reactive cobalt source was cobalt (II) sulfate for examples 62A to 70A and cobalt (II) acetate for examples 71A to 83A.

Samples of the products were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the CoAPSO was prepared being given in parenthesis after the designation of the CoAPSO species.

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clean crystals of CoAPSO products. Analysis of crystals having a morphology characteristic of the CoAPSO compositions noted hereinafter gave the following analysis based on relative peak heights:

Samples of the CoAPSO products were tested for adsorption capacities. The CoAPSO products were evaluated either in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned calcined CoAPSO products were:

(c) The species denominated herein as CoAPSO-5 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" are the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX-A:

(c) The species denominated herein as CoAPSO-11 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII-A:

(b) The species denominated herein as CoAPSO-16 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVI-A:

(c) The species denominated herein as CoAPSO-20 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2 where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XX-A:

(c) The species denominated herein as CoAPSO-31 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIV-A:

(c) The species denominated herein as CoAPSO-34 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions, being as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXVIII-A:

(c)(The species denominated herein as CoAPSO-35 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of zero to about 0.3; "w" , "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXII-A:

(c) The species denominated herein as CoAPSO-36 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXVI-A:

(b) The species denominated herein as CoAPSO-39 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on any anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXIX-A:

(c) The species denominated herein as CoAPSO-44 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2 where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz)O2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXXIII-A:

(b) The species denominated herein is CoAPSO-46 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz) and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXXVI-A:

(c) The species denominated herein as CoAPSO-47 has a three-dimensional microporous crystal framework structure of CoO2, AlO2, PO2 and SiO2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cow Alx Py Siz)O2 where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Cow Alx Py Siz) and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table LI-A:

In order to demonstrate the catalytic activity of the CoAPSO compositions, calcined samples of the CoAPSO products were tested for catalytic cracking by n-butane cracking.

The n-butane cracking was carried out using a bench scale rector. The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test CoAPSO's which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the CoAPSO had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C., for one hour. In some instances, samples were calcined in situ. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of the CoAPSO compositions. The kA value (cm3 /g min) obtained for the CoAPSO compositions are set forth, below.

The MgAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:

eR:fMgO:hAl2 O3 :iP2 O5 :gSiO2 :jH2 O

wherein e, f, g, h, i and j represent the moles of template R, magnesium (expressed as the oxide, SiO2, Al2 O3, P2 O5 (H3 PO4 expressed as P2 O5) and H2 O, respectively. The values for E, f, g, h, i and j were as set forth in the hereinafter discussed preparative examples.

The reaction mixtures were prepared by three procedures, designated hereinafter as Methods A, B and C, unless otherwise noted in the preparative examples.

Method A was employed for examples 1B to 25B, 27B-30B, 39B-46B, 55B-57B, 61B, 63B-71B, 77B-85B and 87B-106B. Method B was employed for examples 31B-38B and 47B-54B. Method C was employed for examples 26B, 62B and 72-76B. The aluminum source was aluminum iso-propoxide except that CATAPAL was the aluminum source in examples 39B-55B and 58B-61B.

Method A

The reaction mixture was prepared by mixing the ground aluminum source (Al-ipro or CATAPAL) with the H3 PO4 and water on a gradual basis with occasional cooling with an ice bath. The resulting mixture was blended until a homogeneous mixture was observed. When the aluminum source was CATAPAL the water and H3 PO4 were first mixed and the CATAPAL added thereto. The magnesium actate was dissolved in portion of the water and was then added followed by addition of the LUDOX-LS. The combined mixture was blended until a homogeneous mixture was observed. The organic templating agent was added to this mixture and blended until a homogeneous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C. or 200° C.) for an effective time. Alternatively, if the digestion temperature was 100° C., the final reaction mixture was placed in a lined (polytetrafluoroethylene) screw top bottle for a time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

Method B

When method B was employed the organic templating agent was di-n-propylamine. The aluminum source, silicon source and one-half of the water were first mixed and blended until a homogeneous mixture was observed. A second solution was prepared by mixing the remaining water, the H3 P4 and the magnesium acetate. This solution was then added to the above mixture. The magnesium acetate and H3 PO4 solution was then added to the above mixture and blended until a homogeneous mixture was observed. The organic templating agent(s) was then added and the resulting reaction mixture digested and product recovered as was done in Method A.

Method C

Method C was carried out by mixing aluminum isopropoxide, LUDOX LS and water in a blender or by mixing water and aluminum iso-propoxide in a blender followed by addition of the LUDOX LS. H3 PO4 and magnesium acetate were then added to this mixture. The organic templating agent was then added to the resulting mixture and digested and product recovered as was done in Method A.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof.

EXAMPLES 1B TO 90B and AB to QB

MgAPSO molecular sieves were prepared according to the above described Methods A, B and C by preparing reaction mixtures expressed as

eR:fMgO:hAl2 O3 :iP2 O5 :gSiO2 :jH2 O

wherein, e, f, h, i, g and j represent the moles of template R, magnesium (expressed as the oxide), Al2 O3, SiO2, P2 O5 (H3 PO3 expressed as P2 O5), and H2 O respectively. The values for e, f, g, h and i for examples 1B to 90B are set forth in Table I-B to VI-B. The value of "j" was 50 in examples 1B to 84B and 87B-90B and was 75B in example 85B and was 7B in example 86B. Tables IB to VI-B also shows the temperature (°C.) and time (hours) employed for digestion and indicates the final MgAPSO(s) formed.

Examples AA to QB represent reaction mixtures wherein crystalline MgAPSO products were not observed when the reaction products were subjected to X-ray analysis. The results of Examples AB to QB are set forth in Table VII-B.

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of examples. Analysis of crystals having a morphology characteristic of the MgAPSO products as prepared in the following referenced examples gave the following analysis based on relative peak heights:

Samples of the MgAPSO products were evaluated for adsorption capacities in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each as-synthesized or calcined sample were measured using a standard McBain - Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C., prior to measurements. The McBain-Bakr data for the selected MgAPSO products were:

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

EXAMPLE 110B

(a) MgAPSO-5, as prepared to in example 4B, was subjected to X-ray analysis. MgAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The MgAPSO-5 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern below in Table X-B, below:

(a) MgAPSO-11, as prepared to in example 17B, was subjected to x-ray analysis. MgAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The MgAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XII-B, below:

(a) MgAPSO-16, as prepared to in example 93B, was subjected to x-ray analysis. MgAPSO-16 was determined to have a characteristic x-ray powder diffraction patterm which contains the d-spacings set forth below:

(d) The MgAPSO-16 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIV-B, below

(a) MgAPSOP-20, as prepared in example 98B, was subjected to x-ray analysis. MgAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The MgAPSO-20 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVI-B, below:

(a) MgAPSO-34, as prepared in example 68B, was subjected to x-ray analysis. MgAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The MgAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVIII-B below.

(a) MgAPSO-35, as prepared in example 85B, was subjected to x-ray analysis. MgAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The MgAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XX-B, below:

(a) The MgAPSO-36, as prepared in example 5B, was subjected to x-ray analysis. MgAPSO-36 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(b) A portion of the as-synthesized MgAPSO-36 of part (a) was calcined in air at 500° C. for about 2 hours and at 600° C. for an additional 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

(d) The MgAPSO-36 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXII-B below:

(a) MgAPSO-39, as prepared in example 55B, was subjected to x-ray analysis. MgAPSO-39 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The MgAPSO-39 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIV-B below.

(a) MgAPSO-43, as prepared in example 92B, was subjected to x-ray analysis. MgAPSO-43 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(b) A portion of the as-synthesized MgAPSO-43 of part (a) was calcined in air at 500° C. for about 1 hour and at 600° C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

(d) The MgAPSO-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXVI-B below:

(c) MgAPSO-44, as prepared in example 88B, was subjected to X-ray analysis. MgAPSO-44 was determined to have a characteristic X-ray powder diffraction pattern which contains the d-spacings set forth below:

(b) A portion of the as-synthesized MgAPSO-44 of part (a) was calcined in air for 2.5 hours at 500° C. and then for 0.25 hour at 600° C. The calcined product was characterized by the x-ray powder diffraction pattern below:

(a) The MgAPSO-46, as prepared in example 44B, was subjected to x-ray analysis. MgAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(b) A portion of the as-synthesized MgAPSO-46 of part (a) was calcined in nitrogen at 500° C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

(d) The MgAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXX-B below:

(a) MgAPSO-47, as prepared in example 104B, was subjected to x-ray analysis. MgAPSO-47 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The MgAPSO-47 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXXII-B below.

In order to demonstrate the catalytic activity of the MgAPSO compositions, calcined samples of MgAPSO products were tested for catalytic cracking of n-butane using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test MgAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the confession n-butane was at least 5% and not more than 90% under the test conditions. The MgAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed for 10 minutes of on-stream operation.

The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of the MgAPSO compositions. The kA value (cm3 /g min) obtained for the MgAPSO compositions are set forth, below, in Table XXX-B:

TABLE XXX-B______________________________________ Prepared inMgAPSO Example No. Rate Constant (k.sub.A)*______________________________________MgAPSO-35 80B 2.6MgAPSO-34 63B 4.1MgAPSO-35 82B 0.9MgAPSO-36 5B 18.0MgAPSO-46 44B 7.3MgAPSO-47 104B 1.7______________________________________ *Prior to activation of the MgAPSO samples of the following examples such were calcined as follows: (a) Example 80B: calcined in air at 600° for 2.25 hours; (b) Example 63B: calcined in air at 550° C. for 2 hours; (c) Example 82B: calcined in nitrogen at 425° C. for 2 hours; (d) Example 5B: calcined in air at 500° C. for 2 hours and then at 600° C. for 2 hours; (e) Example 44B: calcined in nitrogen at 500° C. for 1.75 hours; and (f) Example 104B: calcined in air at 500° C. for 1.75 hours.

(a) Examples 1C to 8C were carried out to demonstrate the preparation of FEAPSO-34 and FeAPSO-5. The reaction mixtures wer prepared by grinding the aluminum isopropoxide in a blender followed by slowly adding the H3 PO4 solution with mixing. A solution/dispersion of iron acetate in water was added and then the LUDOX-LS was added. The organic templating agent was then added to this mixture, or in some cases one-half of this mixture, and the mixture blended to from a homogeneous mixture. The number of moles of each component in the reaction mixture was as follows:

Each reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at a temperature (see Table I-C), time (see Table I-C) and at the autogeneous pressure. The solid reaction product was recovered by filtration, washed with water and dried at room temperature. The products were analyzed and th observed FeAPSO products reported in Table I-C.

(c) Examples 9C to 16C were carried out to demonstrate the preparation of FeAPSO-11 and FeAPSO-5. The reaction mixtures were prepared by grinding the aluminum iso-propoxide in a blender followed by addition of a solution/dispersion of Iron (II) acetate. H3 PO4 was added to this mixture and the resulting mixture blended to form a homogeneous mixture. LUDOX-LS was added to this mixture except that in examples 13C to 16C the LUDOX-LS were added with H3 PO4. The resulting mixtures were blended until a homogeneous mixture was observed. Organic templating agent was added to each mixture and the resulting mixtures placed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated. Washed and the product recovered as in part (a) of this example. The products were analyzed and the observed FeAPSO products reported in Table I-C. The number of moles of each component in the reaction mixture was as follows:

(c) Two reaction mixtures, designated Example AC and BC in Table I-C, did not show FeEAPSO products when analyzed by X-ray. Examples AC and BC followed the same procedure employed for Example 5C and 6C.

Example 15C to 19C were carried out according to the general preparative procedure employed for example 7C to 14C with examples 15C to 18C following the procedure employed for examples 7C to 10C and example 19C following the procedure followed for examples 11C to 14C. The reactive source of iron was Iron (II) sulfate instead of Iron (II) acetate. The temperature and time for the crystallization (digestion) procedure are set forth in Table II-C.

The number of moles of each component in the reaction mixture for examples 15C to 18C was as follows:

Examples 28C and 29C were carried out according to the procedure of examples 13C to 16C. except that Iron (II) sulfate, was employed as the reactive iron source instead of Iron (II) acetate. The number of moles of each component in the reaction mixture for each example was as follows:

Examples CC and DC followed the procedure for examples 28C and 29C. X-ray analysis of the reaction procuts did not show FeAPSO products.

The temperature and time for the crystallization procedure and the observed FeAPSO products are reported in Table IV-C.

TABLE IV-C______________________________________ TempExample Template (°C.) Time (hr.) FeAPSO Product.sup.1______________________________________28C TBAOH 200 49 FeAPSO-529C TBAOH 200 161 FeAPSO-5 CC TBAOH 150 49 --DC TBAOH 150 161 --______________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the major species observed. A "--" indicates no FeAPSO product was present as determined by Xray analysis.

EXAMPLES 30C TO 43C

Examples 30C to 43C were carried out according to the procedure employed for examples 1C to 8C except that in examples 30C and 31C the aluminum source was CATAPAL and in examples 33C to 36C and 43C a seed crystal of a topologically similar molecular sieve was employed. The number of moles of each component in the reaction mixture in examples 30C to 43C was:

(a) Samples of FeAPSP products were calcined at 600° C. in air for 2 hours to remove at least part of the organic templating agent, except that FeAPSO-5 and FeAPSO-11 were calcined for 2.25 hours. The example in which the FeAPSO was prepared is indicated in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the FeAPSO compositions are set forth hereinafter.

EDAX (energy dispersive analysis by X-ray) microprobe analysis in conjunction with SEM (scanning electron microscop) was carried out on clear crystals ofFEAPSP products of the hereinafter designated examples. Analysis of crystals having a morphology characteristic of FeAPSO-5, FeAPSO-11, FeAPSO-20, FeAPSO-31, FeAPSO-34 and FeAPSO-46 gave the following analysis based on relative peak heights:

(a) FeAPSO-5, as prepared in example 12C, was subjected to x-ray analysis. FeAPSO-5 was determined to have a characteristic x-ray powder diffaction pattern which contains the d-spacings set forth below:

(b) A portion of the as-synthesized FeAPSO-5 of part (a) was calcined in air at a temperature beginning at 500° C. and ending at 600° C. over a period of 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

(a) FeAPSO-11, as prepared in example 10C, was subjected to x-ray analysis. FeAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(a) FeAPSO-16, as prepared in example 21C, was subjected to x-ray analysis. FeAPSO-16 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(a) FeAPSO20, as prepared to in example 31C, was subjected to x-ray analysis. FeAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(b) A portion of the as-synthesized FeAPSO-20 of part (a) was calcined in air heating the sample from 500° C. to 600° C. over a period of 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

(a) FeAPSO-31, as prepared in example 34C, was subjected to x-ray analysis. FeAPSO-31 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(a) FeAPSO-34, as prepared in example 3C, was subjected to x-ray analysis. FeAPSO-34 was determined to have a charactristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(a) FeAPSO-35, as prepared in example 27C, C was subjected to x-ray analysis. FeAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(a) FeAPSO-44, as prepared in example 32C, was subjected to x-ray analysis. FeAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(a) FeAPSO-46, as prepared in example 38C was subjected to x-ray analysis. FeAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(d) The FeAPSO-46 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIII-C below:

In order to demonstrate the catalytic activity of the FeAPSO compositions, calcined samples of FeAPSO products were tested for the catalytic cracking of n-butane using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the selected FeAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium and n-butane mixture containing 2 mole percent n-butane and was passes through the reactor at a rate of50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of the FeAPSO compositions. The kA value (cm3 /g min) obtained for the FeAPSO compositions are set forth, below, in Table XXIV-C:

The following preparative examples were carried out by forming a starting reaction mixture by adding the H3 PO4 to one half of the quantity of water. This mixture was mixed and to this mixture the aluminum isopropoxide or CATAPAL was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed. A second mixture was prepared using the manganese acetate and the remainder (about 50%) of the water. The two mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. (The pH of the mixture was measured and adjusted for temperature). The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C. or 200° C.) for a time or placed in lined screw top bottles for digestion at 100° C. All digestions were carried out at the autogeneous pressure.

The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture with H3 PO4 and MnAc are given respectively in terms of P2 O5 and MnO content of the reaction mixture.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof;

EXAMPLES 1D TO 64D

MnAPSO molecular sieves were prepared according to the above identified procedure and the MnAPSO products determined by X-ray analysis. The results of examples 1D to 64D are set forth in Tables I-D to IV-D.

(a) Samples of the MnAPSO products were calcined in air or nitrogen to remove at least part of the organic templating agent of the product. The example in which a given MnAPSO product was prepared is given in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned MnAPSO molecular sieves are set forth hereinafter.

The above data demonstrate that the pore size of the calcined MnAPSO-44 product about 4.3 Å.

EXAMPLE 66D

Samples of the as-synthesized products of certain examples were subjected to chemical analysis. The example in which a given MnAPSO was prepared is noted in parenthesis. The chemical analysis for these MnAPSO was as follows:

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of certain examples, as identified in parenthesis hereinafter. Analysis of crystals having a morphology characteristic of each MnAPSO product gave the following analysis based on relative peak heights:

(a) The MnAPSO-5, prepared in Example 31D, was subjected to x-ray analysis. The MnAPSO-5 was impure but the major phase was determined to have an x-ray powder diffraction pattern characterized by the following data:

(b) A portion of the as-synthesized MnAPSO-5 of part (a) was calcined in air at 500° C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-5 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)Oz wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-5 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V-D as follows:

(d) All of the MnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VI-D below:

(b) A portion of the as-synthesized MnAPSO-11 of part (a) was calcined in air at 600° C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-11 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-11 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII-D as follows:

(d) All of the MnAPSO-11 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtained have patterns which are within the generalized pattern of Table VIII-D below:

(b) A portion of the as-synthesized MnAPSO-16 of part (a) was calcined in nitrogen at 600° C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-16 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points, a, b, c and d of FIG. 2, said MnAPSO-16 having a characterized x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX-D as follows:

(d) All of the MnAPSO-16 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table X-D below:

(c) The species denominated herein as MnAPSO-20 is a molecular sieve having a three dimensional microporous sieve having a three structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-20 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI-D as follows:

(d) All of the MnAPSO-20 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XII-D below:

(c) The species denominated herein as MnAPSO-31 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present an tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-31 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII-D as follows:

(d) All of the MnAPSO-31 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV-D below:

(b) A portion of the as-synthesized MnAPSO-34 of part (a) was calcined in nitrogen at 425° C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-34 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represent at least one organic templating agent present in the intracrystalline pore system; "m" represent the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-34 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV-D as follows:

(d) All of the MnAPSO-34 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV-D below:

(b) A portion of the as-synthesized MnAPSO-35 of part (a) was calcined in nitrogen at 500° C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-35 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-35 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVII-D as follows:

(d) All of the MnAPSO-35 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XVIII-D below:

(c) The species denominated herein as MnAPSO-36 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2- and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-36 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX-D as follows:

(d) All of the MnAPSO-36 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized patter of Table XX-D below:

(b) A portion of the as-synthesized MnAPSO-44 of part (a) was calcined in air at 500° C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-44 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Mnw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-44 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXI-D as follows:

(d) All of the MnAPSO-44 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXII-D below:

(b) A portion of the as-synthesized MnAPSO-47 of part (a) was calcined in air at 500° C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:

(c) The species denominated herein as MnAPSO-47 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO2-2, AlO2-, PO2+ and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR: (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system: "m" represents the molar amount of "R" present per mole of (Mnw Alx Py Siz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-47 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII-D as follows:

(d) All of the MnAPSO-47 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXIV-D below:

The catalytic activity was determined using a reactor comprising a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test MnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the MnAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium- n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of the MnAPSO compositions. The kA value (cm3 /g min) obtained for the MnAPSO compositions are set forth, below, in Table XXV-D:

TABLE XXV-D______________________________________ Prepared in RateMnAPSO Example No. Constant (k.sub.A)*______________________________________MnAPSO-5 31D 0.2MnAPSO-11 25D 0.6MnAPSO-20 46D 0.2MnAPSO-31 55D 1.0; 0.5MnAPSO-34 11D 3.1MnAPSO-35 21D 0.1**MnAPSO-36 59D 0.3MnAPSO-44 64D 1.5MnAPSO-47 49D 1.7______________________________________ *Prior to determination of the catalystic activity of a given MnAPSO, eac was calcined as follows: a) MnAPSO5 was calcined at 500° C. in air for 2 hours; b) MnAPSO11, MnAPSO34 and MnAPSO36 were calcined in situ; c) MnAPSO31 was calcined in air at 500° C. for 1.5 hours and then at 600° C. for 1 hour; d) MnAPSO35 was calcined at 500° C. in nitrogen for 1 hour; and e) MnAPSO20, MnAPSO44 and MnAPSO47 were calcined at 500° C. in air for 1 hour. **Less than 0.1

The following preparative examples were carried out by forming a starting reaction mixture by adding the H3 PO4 and the water. This mixture was mixed and to this mixture the aluminum isoproxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed.

The titanium isopropoxide was added to the above mixture and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. When the organic templating agent was quinuclidine the procedure was modified such that the quinuclidine was dissolved in about one half the water and accordingly the H3 PO4 was mixed with about one half the water. (The pH of the mixture was measured and adjusted for temperature). The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150° C. or 200° C.) for a time or placed in lined screw top bottles for digestion at 100° C. All digestions were carried out at the autogeneous pressure.

The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture. H3 PO4 and titanium isopropoxide are given respectively in terms of the P2 O5 and TiO2 content of the reaction mixture.

All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

EXAMPLES 1E to 30E

TiAPSO molecular sieves were prepared according to the above described preparative procedure and the TiAPSO products determined by x-ray analysis. The results of examples 1E to 30E are set forth in Tables I-E and II-E.

Samples of the products of examples 4E, 6E, 15E, 24E and 30E were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the TiAPSO was prepared being given in parenthesis after the designation of the TiAPSO species.

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope was carried out on clear crystals from the products of example 4E, 11E, 12E, and 21E. Analysis of crystals having a morphology characteristic of TiAPSO compositions gave the following analysis based on relative peak heights:

Samples of the TiAPSO products of examples 4E, 13E, and 6E were evaluated for adsorption capacities in the calcined form by calcination in air to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned calcined TiAPSO products were:

The above data demonstrate that the pore size of the calcined product is greater than 6.2 Å.

EXAMPLE 34E

(a) TiAPSO-5 compositions, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table III below:

(a) TiAPSO-11, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII-E below:

(a) TiAPSO-16, as referred to herein in both the as-synthesized and calcined form, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI-E below:

(a) TiAPSO-34, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV-E below:

(a) TiAPSO-35, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX-E below:

(d) The calcined TiAPSO-35 compositions of example 2E was calcined at 600° C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XXII-E, below.

(a) TiAPSO-44, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII-E below:

In order to demonstrate the catalytic activity of the TiAPSO compositions, calcined samples of the TiAPSO products of Examples 6E, 13E, and 24E were tested for catalytic cracking of n-butane.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test TiAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The TiAPSO samples were calcined in air (TiAPSO-5 at 600° C. for 2.5 hours; TiAPSO-11 at 600° C. for 1.5 hours; and TiAPSO-34 at 500° C. for 2 hours) to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation. The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of the TiAPSO compositions. The kA value (cm3 /g min) obtained for the TiAPSO compositions are set forth, below, in Table XXVI-E:

The ZnAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:

eR:fZnO:gAl2 O3 :hP2 O5 :iSiO2 :jH2 O

wherein e, f, g, h, i and j represent the moles of template R, zinc (expressed as the oxide), Al2 O3, P2 O5 (H3 PO4 expressed as P2 O5), SiO2 and H2 O, respectively. The values for e, f, g, h, i and j were as set forth in the hereinafter discussed preparative examples where "j" was 50 in each example, and "e" was 1.0.

The reaction mixtures were prepared by forming a starting reaction mixture comprising the H3 PO4 and a portion of the water. This mixture was stirred and the aluminum source added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX LS was then added to the resulting mixture and the new mixture blended until a homogeneous mixture was observed. The zinc source (zinc acetate) was dissolved in the remaining water and combined with the first mixture. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a liner (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.

EXAMPLES 1F to 41F

ZnAPSO molecular sieves were prepared according to the above described procedure and the ZnAPSO products determined by x-ray analysis. The results of preparative examples 1F to 41F are set forth in Tables I-F and II-F. The reactive zinc source was zinc acetate. The reactive aluminum source was Alipro. The reactive phosphorus source was H3 PO4, the reactive silicon source was LUDOX-LS. The organic templating agents are set forth in Tables I-F and II-F.

Samples of the products of examples 4F, 17F, 24F, 33F, 35F and 39F were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the ZnAPSO was prepared being given in parenthesis after the designation of the ZnAPSO species.

EDAX (energy dispersive analysis by x-ray microprobe analysis in conjunction with SEM (scanning electron microscope was carried out on clear crystals from the products of examples 4F, 24F, 33F, 35F and 39F. Analysis of crystals having a morphology characteristic of the ZnAPSO products gave the following analysis based on relative peak heights:

Samples of the ZnAPSO products of examples 4F, 27F, 33F, 35F and 39F were for adsorption capacities evaluated in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350° C. prior to measurement. The McBain-Bakr data for the aforementioned calcined ZnAPSO products were:

The above data demonstrate that the pore size of the calcined product is about 4.3 Å.

EXAMPLE 45F

(a) ZnAPSO-5, as prepared in example 4F, was subjected to x-ray analysis. ZnAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(b) A portion of the as-synthesized ZnAPSO-5 of part (a) was calcined in air at 500° C. for about 0.75 hours and then in air at 600° C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:

(d) The ZnAPSO-5 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table IV-F, below.

(a) ZnAPSO-11, as prepared in example 10F was subjected to x-ray analysis. ZnAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VI-F, below:

(a) ZnAPSO-20, as prepared in example 29F, was subjected to x-ray analysis. ZnAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-20 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VIII-F, below:

(a) ZnAPSO-31, as prepared in example 14F, was subjected to x-ray analysis. ZnAPSO-31 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-31 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table X-F, below:

(a) ZnAPSO-34, as prepared in example 24F, was subjected to x-ray analysis. ZnAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(d) The ZnAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XII-F, below:

(a) ZnAPSO-35, as prepared in example 33F, was subjected to x-ray analysis. ZnAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(d) The ZnAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIV-F below:

(a) ZnAPSO-36, as prepared in example 1F, was subjected to x-ray analysis. ZnAPSO-36 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-36 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVI-F below:

(a) ZnAPSO-39, as referred to in example 9F, was subjected to x-ray analysis. ZnAPSO-39 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-39 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVIII-F below:

(a) ZnAPSO-43, as referred to in example 28F, was subjected to x-ray analysis. ZnAPSO-43 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XX-F below:

(d) The ZnAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXII-F below:

(a) ZnAPSO-46, as referred to in example 8F was subjected to x-ray analysis. ZnAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(c) The ZnAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIV-F below:

(a) ZnAPSO-47, as referred to in example 38F, was subjected to x-ray analysis. ZnAPSO-47 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

(d) The ZnAPSO-47 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXVI-F below:

In order to demonstrate the catalytic activity of calcined ZnAPSO compositions were tested for catalytic cracking of n-butane using a bench-scale apparatus.

The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the test ZnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The ZnAPSO samples had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of the ZnAPSO compositions. The kA value (cm3 /g min) obtained for the ZnAPSO compositions are set forth, below, in Table XXVII-F:

TABLE XXVII-F______________________________________ Prepared inZnAPSO Example No. Rate Constant (k.sub.A)*______________________________________ZnAPSO-5 4F 1.5ZnAPSO-34 24F 12.7ZnAPSO-35 33F 1.0ZnAPSO-44 35F 5.0ZnAPSO-47 39F 5.6______________________________________ *ZnAPSO were calcined prior to in situ activation as follows: (a) ZnAPSO5: in air at 500° C. for 0.75 and at 600° C. for 1.25 hours; (b) ZnAPSO34: in air at 500° C. for 2 hours; (c) ZnAPSO35: in air at 500° C. for 1.75 hours; (d) ZnAPSO44: in air at 500° C. for 67 hours; and (e) ZnAPSO47: in air at 500° C. for 1.75 hours.

The following preparative examples were carried out by forming a starting reaction mixture by adding the H3 PO4 and one half of the quantity of water. To this mixture the aluminum isopropoxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed. A second mixture was prepared using manganese acetate and one half of the remaining water. A third mixture was prepared using cobalt acetate and one half of the remaining water. The three mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e. about 2 to 4 minutes. The pH of the mixture was measured and adjusted for temperature. The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature. All digestions were carried out at the autogeneous pressure.

EXAMPLES 1G TO 4G

CoMnAPSO molecular sieves were prepared according to the above identified procedure and the CoMnAPSO products determined by X-ray analysis. The results of examples 1G to 4G are set forth in Table I-G. Examples AG to FG in Table I-G represent reaction mixtures that did not show CoMnAPSO products when determined by X-ray analysis.

(a) Samples of the above prepared CoMnAPSO products, as identified in parenthesis, were calcined in air to remove at least part of the organic templating agent of the CoMnAPSO product. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350° C. prior to measurement. The McBain-Bakr data were as follows:

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on the products of example 2G and 4G. Analysis of crystals having a morphology characteristic of each CoMnAPSO product gave the following analysis based on relative peak heights:

(d) All of the CoMnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have been obtained have patterns which are within the generalized pattern of Table III-G, below:

(a) The CoMnAPSO-11, prepared in example 3G, was subjected to X-ray analysis. The CoMnAPSO-11 was impure but the CoMnAPSO-11 was determined to have an X-ray powder diffraction pattern characterized by the following data:

(d) All of the CoMnAPSO-11 compositions both as-synthesized and calcined, for which x-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern on Table V-G, below:

(a) The CoMnAPSO-34, prepared in example 1G, was subjected to x-ray analysis. The CoMnAPSO-34 was impure but was the major phase and was determined to have an x-ray powder diffraction pattern characterized by the following data:

In order to demonstrate the catalytic activity of the CoMnAPSO compositions, calcined samples of the products of examples 2G and 4G, were tested for catalytic cracking. The CoMnAPSO compositions were evaluated for n-butane cracking using a bench-scale apparatus.

The reactor was cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the CoMnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The CoMnAPSO samples had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (kA) was calculated to determine the relative catalytic activity of each CoMnAPSO composition. The kA value (cm3 /g min) obtained for the CoMnAPSO are set forth below:

The following preparative examples were carried out by forming a starting reaction mixture by adding the H3 PO4 and one half of the quantity of water. To this mixture the aluminum isoproxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed.

Three additional mixtures were prepared using cobalt acetate, magnesium acetate and manganese acetate using one third of the remainder of the water for each mixture. The four mixtures were then admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 mixtures. The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature for a time. All digestions were carried out at the autogeneous pressure.

The molar composition for each preparation will be given by the relative moles of the components with H3 PO4 be given as P2 O5.

EXAMPLES 1H TO 4H

CoMnMgAPSO molecular sieves were prepared according to the above identified procedure and the CoMnMgAPSO products determined by X-ray analysis. The results of preparative examples 1H to 4H are set forth in Table I-H. Examples AH, BH and CH of Table I-H did not contain a product identifiable by x-ray analysis.

Portions of the products of examples 3H and 4H were calcined in air at 600° C. for 1.5 hour to remove at least part of the organic templating agent. The adsorption capacities of each calcined sample were measured using a standard McBain-Baker gravimetric absorption apparatus. The samples were activated in a vacuum (less than about 0.04 torr) at 350° C. prior to measurement. The McBain-Baker data for the CoMnMgAPSO products were:

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clean crystals of products from examples 3H and 4H. Analysis of crystals having a morphology characteristic of CoMnMgAPSO-5, CoMnMgAPSO-11, and CoMnMgAPSO-34 gave the following analysis based on relative peak heights:

(a) CoMnMgAPSO-5, as prepared to in example 3H, was subjected to x-ray analysis and was determined to have a characteristics x-ray powder diffraction pattern which contains the d-spacings set forth below:

(c) The species CoMnMgAPSO-5 is a molecular sieve having a three-dimensional microporous framework structure of CoO2-2, MnO-2-2, MgO2-2, AlO2-, PO2+, and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cot Mnu Mgv Alx Py Siz)O2

where "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of Cot Mnu Mgv Alx Py Siz)O2 and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table II-H:

(a) CoMnMgAPSO-11, as prepared in example 4H was subjected to x-ray analysis. CoMnMgAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:

(c) The species CoMnMgAPSO-11 is a molecular sieve having a three-dimensional microporous framework structure of CoO2-2, MnO2-2, MgO2-2, AlO2-, PO2+, and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(Cot Mnu Mgv Alx Py Siz)O2 where "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cot Mnu Mgv Alx Py Siz)O2 and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder pattern which contains at least the d-spacings set forth in Table IV-H:

(a) CoMnMgAPSO-34, as prepared in example 3H was subjected to x-ray analysis. CoMnMgAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains ao least the d-spacings set forth below:

(c) The species CoMnMgAPSO-34 is a molecular sieve having a three-dimensional microporous framework structure of CoO2-2, MnO2-2, MgO2-2, AlO2-, PO2+, and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(Cot Mnu Mgv Alx Py Siz)O2

where "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of Cot Mnu Mgv Alx Py Siz)O2 and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VI-H:

The catalytic activity of the CoMnMgAPSO compositions of examples 3H and 4H were evaluated in n-butane cracking using a bench-scale apparatus.

The reactor was cylindrical quartz tube 254 mm. in length an 10.3 mm. I.D. In each test the reactor was loaded with particles of the test CoMnMgAPSO's which were 20-40 mesh (U.S. Std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The CoMnMgAPSO samples were calcined in air at 600° C. for 1.5 hours to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500° C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation. From the analytical data the pseudo-first-order rate constants (kA ) were calculated and are set forth in Table VIII-H below:

The ELAPSO compositions of the instant invention exhibit novel surface selectivity characteristics where render them useful as catalysts or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods were known in the art and used, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4 Å are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by ELAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.

Using ELAPSO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400° F. to 825° F. using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.

The ELAPSO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700° F. to 1000° F., hydrogen pressures of from 100 to 500 p.s.i.g., LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerizations processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200° F. to 600° F., preferably 300° F. to 550° F. with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixture with the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F., preferably 850° F. to 950° F. and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C7 -C20. Contact time between the feedstock and the catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.

The unique crystal structures of the present ELAPSO catalysts and their availability in a form having very low alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition. Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400° to 750° F., pressures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with ELAPSO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850° to 1100° F., LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the ELAPSO catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.

In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800°-1000° F. are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like any of which may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than are required with a feed containing less organonitrogen compounds. Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compound on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening testing with the specific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500°-900° F., while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700°-1000° F. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the ELAPSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the ELAPSO compositions having pores of at least 5 Å are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350° F. and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700° F. The temperature is preferably at least 450° F. and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low as 250° F. but is preferably at least 350° F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.

Claims (6)

We claim:

1. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a molecular sieve, said molecular sieve being a crystalline molecular sieve having three-dimensional microporous framework structures of ELO2, AlO2, PO2, SiO2 oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

mR:(ELw Alx Py Siz)O2

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ELw Alx Py Siz)O2 and has a value of zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework, "EL" is characterized as an element having a mean "T--O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/g-atom and "EL" is capable of forming stable M--O--P, M--O--Al or M--O--M bonds in crystalline three dimensional oxide structures having an "M--O" bond dissociation energy greater than about 59 kcal/mole at 289° C.; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus, and silicon, respectively, present as framework oxides, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, wherein element "EL" and each of aluminum, phosphorus and silicon are present such that "w", "x", "y" and "z" are at least 0.01 and each element "EL" is present as a tetrahedral oxide unit ELO2 in an amount of at least 0.01.

2. Process according to claim 1 wherein the mole fractions "w", "x", "y" and "z" are within the tetragonal compositional area defined by points a, b, c and d of FIG. 2.

3. Process according to claim 1 wherein, before being contacted with said hydrocarbon, said molecular sieve is calcined at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system.

4. Process according to claim 1 wherein said crystalline molecular sieve has a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set fourth in one of Tables A to H and J to W